WO2012116515A1 - 一种可降解塑料及其生产方法 - Google Patents

一种可降解塑料及其生产方法 Download PDF

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WO2012116515A1
WO2012116515A1 PCT/CN2011/073174 CN2011073174W WO2012116515A1 WO 2012116515 A1 WO2012116515 A1 WO 2012116515A1 CN 2011073174 W CN2011073174 W CN 2011073174W WO 2012116515 A1 WO2012116515 A1 WO 2012116515A1
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straw
plastic
degradable
crop
acid amide
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PCT/CN2011/073174
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English (en)
French (fr)
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殷正福
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江苏锦禾高新科技股份有限公司
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Priority to US13/882,883 priority Critical patent/US9051466B2/en
Publication of WO2012116515A1 publication Critical patent/WO2012116515A1/zh

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00Compositions of lignin-containing materials
    • C08L97/02Lignocellulosic material, e.g. wood, straw or bagasse
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the invention relates to a degradable plastic and a production method thereof, in particular to a degradable plastic using crop straw as a raw material and a production method thereof.
  • Crop straw refers to waste in agricultural production and is usually incinerated. This method not only wastes the potential value of crop straw, but also causes air pollution. The smoke generated during the incineration will block the line of sight and cause a safety hazard. The flame during incineration may also cause a fire.
  • the object of the present invention is to invent a crop plastic to reduce environmental pollution caused by the abandonment of non-degradable plastics, and to collect crop straw for use.
  • the invention consists of degradable plastics, crop straws and plastic auxiliaries, and the degradable plastics, crop straws and plastic auxiliaries account for 63 ⁇ 73%, 23 ⁇ 33% and 4 ⁇ 6% of the total mass of the raw materials, respectively.
  • the degradable plastic is any one of polylactic acid (PLA) or polybutylene succinate (PBS).
  • PCL polycaprolactone
  • PHA polyhydroxyalkanoate
  • the crop straw is at least any one of straw straw, wheat straw, bran, corn cob, and corn stover.
  • the plastic auxiliary agent is at least any one of a silane coupling agent, an aluminate/titanate composite coupling agent, ethylene bisstearic acid amide, and titanium white powder.
  • the processing temperature of the invention is low, and only needs to be formed at 140 ° C to 160 ° C.
  • the heat-resistant temperature of the invention can reach 80 ⁇ 100 °C, which fully satisfies the general use requirements.
  • the invention can replace daily plastics such as polypropylene, and manufacture daily articles, tableware, containers, stationery, plastic bags, and the like by a film forming method such as blown film, pull-tab, and injection molding.
  • the plastic product produced by the invention as a raw material exhibits the color of natural wood, the surface has the texture of plant fiber, and has a good surface finish, high strength, good toughness and comfortable hand. Since the materials used in the present invention are all degradable materials, the present invention is also a degradable material. Among them, the degradation cycle is up to 180 days. Therefore, the degradation cycle of the present invention is also up to 180 days, and is a green material.
  • Another object of the present invention is to provide a method of producing a crop plastic.
  • the straw stalks of mm are mixed with plastic and plastic auxiliaries after drying, and extruded and granulated by twin-screw extruder.
  • plastics, crop straws and plastic auxiliaries account for 63 ⁇ 73% of the total mass of raw materials, respectively. 23 ⁇ 33% and 4 ⁇ 6%.
  • the invention is convenient for production, and the formed pellets are uniform in particle size, stable in state, easy to be further processed and processed, and no need to modify existing equipment.
  • the invention also reduces the cost of degradable plastics while improving the mechanical properties of the degradable plastics, providing conditions for the widespread use of degradable plastics.
  • the straw is broken and the length is 1.5 ⁇ 2.0.
  • the debris of mm is selected from a silane coupling agent and an ethylene bis-stearic acid amide as a plastic additive, mixed with injection-grade polylactic acid, and then extruded and granulated by a twin-screw extruder.
  • a silane coupling agent and an ethylene bis-stearic acid amide as a plastic additive
  • injection-grade polylactic acid accounted for 23 to 33%, 1 to 1.5%, 3 to 4.5%, and 63 to 73%, respectively.
  • the plastic particles produced by this method can be produced by injection molding to produce corresponding injection molded parts.
  • the mechanical properties of the product can be adjusted by adding polybutylene succinate, and the amount added is 10% to 75% of the total mass of the raw materials. Adding more polybutylene succinate will make the product softer. The specific amount of addition needs to be determined according to different product requirements.
  • the product produced from the above plastic particles was subjected to composting conditions for 180 days, and the degradation rate was over 95%.
  • Example 2 blown film grade products
  • the wheat straw and corn stalk are pulverized into 1000-1200 mesh powder, and the aluminate/titanate composite coupling agent, ethylene bis-stearic acid amide and titanium dioxide are used as plastic additives, and the blown film grade polybutan
  • the butylene glycol ester was mixed and extruded and granulated by a twin-screw extruder.
  • wheat straw, corn stalk, aluminate/titanate composite coupling agent, ethylene bis-stearic acid amide, titanium dioxide, blown film grade polybutylene succinate accounted for 10% of the weight of the raw materials. ⁇ 13%, 13 ⁇ 20%, 1 ⁇ 2%, 1.5 ⁇ 2%, 1.5 ⁇ 2%, 63 ⁇ 73%.
  • the plastic particles produced by this method can be produced by blown film forming to produce corresponding film-like articles.
  • the mechanical properties of the product can be adjusted by adding polyhydroxyalkanoate (PHA) and polylactic acid in an amount of 5 to 25%. Adding more polyhydroxyalkanoates and polylactic acid can reduce the softness of the product. The specific amount of addition needs to be determined according to different product requirements.
  • the film product made of the above plastic particles has good gas permeability in addition to the properties of ordinary plastic film, and is particularly suitable for applications where air permeability is impervious to water, such as plastic wrap, diaper inner film, and the like.
  • the product produced from the above plastic particles was subjected to composting conditions for 180 days, and the degradation rate was over 95%.
  • the straw straw, wheat straw, corn cob and bran are pulverized to form a powder of 1000-1200 mesh.
  • Ethylene bis-stearic acid amide and titanium dioxide are used as plastic additives, mixed with the pull-level polylactic acid and then subjected to twin-screw extrusion. Machine extrusion granulation.
  • straw straw, wheat straw, corn cob, bran, ethylene bis-stearic acid amide, titanium dioxide, and lamin-grade polylactic acid accounted for 5 to 8%, 5 to 8%, 5 to 7 of the total mass of raw materials, respectively. %, 8 ⁇ 10%, 1.5 ⁇ 2%, 2 ⁇ 4%, 63 ⁇ 73%.
  • the plastic particles produced by this method can be formed by pulling a sheet to produce a corresponding sheet product.
  • the mechanical properties of the product can be adjusted by adding polycaprolactone (PCL) in an amount of 5 to 15%. Adding more polycaprolactone can make the product softer. The specific amount of addition needs to be determined according to different product requirements.
  • PCL polycaprolactone
  • the product produced from the above plastic particles was subjected to composting conditions for 180 days, and the degradation rate was over 95%.
  • the invention relates to a degradable plastic and a production method thereof, which can form a degradable plastic with uniform granular particles and stable state, and can replace daily plastics such as polypropylene to make daily necessities, tableware, containers, stationery, plastic bags, etc., and has good The surface finish, high strength, good toughness and comfortable hand.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Description

一种可降解塑料及其生产方法 技术领域
本发明涉及一种可降解塑料及其生产方法,尤其涉及一种以农作物秸秆为原料的可降解塑料及其生产方法。
背景技术
随着塑料工业的发展,塑料在日常生活中的应用范围越发广泛,使用量越发巨大。由于这些塑料多为不可降解材料,在消耗大量石油资源的同时,产生的废弃物也会造成巨大的污染。
农作物秸秆是指农业生产过程中的废弃物,通常作焚烧处理。此方法不但浪费了农作物秸秆潜在的价值,还会造成空气污染。焚烧过程中产生的烟雾会阻挡视线,造成安全隐患,焚烧时的火焰还可能引发火灾。
发明内容
本发明的目的在于发明一种农作物塑料,以减少因抛弃不可降解塑料而造成的环境污染,并将收集农作物秸秆加以利用。
本发明由可降解塑料、农作物秸秆和塑料助剂组成,所述可降解塑料、农作物秸秆、塑料助剂分别占原料总质量的63~73%、23~33%和4~6%。
所述可降解塑料为聚乳酸(PLA)或聚丁二酸丁二醇酯(PBS)中的任意一种。
在可降解塑料中,聚己内酯(PCL)和聚羟基脂肪酸酯(PHA)这两种可降解材料可以添加剂的形式出现在配方中,用于调节产品强度。
所述农作物秸秆为稻草秸秆、麦草秸秆、麸皮、玉米芯、玉米秆中的至少任意一种。
所述塑料助剂为硅烷偶联剂、铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺、钛白粉中的至少任意一种。
本发明的加工温度低,仅需140℃~160℃即可成型。本发明的耐热温度可达80~100℃,完全满足一般使用需求。本发明可代替聚丙烯等常规塑料,通过吹膜、拉片、注塑等成型方法制作日常用品、餐具、容器、文具、塑料袋等。由本发明为原材料生产的塑料制品呈现出天然木材的颜色,表面具有植物纤维的纹理,并具有良好的表面光洁度,强度高、韧性好、手感舒适。由于本发明所用原料均为可降解材料,因此本发明也为可降解材料。其中,降解周期最长为180天。因此,本发明降解周期最长也为180天,是一种绿色环保的材料。
本发明的另一目的是提供农作物塑料的生产方法。
将长度为1.5~2.0 mm的农作物秸秆碎屑经干燥后与塑料、塑料助剂混合,经双螺杆挤出机挤出造粒;投料时,塑料、农作物秸秆、塑料助剂分别占原料总质量的63~73%、23~33%和4~6%。
本发明方便生产,形成的粒料颗粒均匀,状态稳定,易于进一步生产加工,且无需对现有设备进行改造。本发明也降低了可降解塑料的成本,同时改善了可降解塑料的力学性能,为可降解塑料的广泛应用提供了条件。
具体实施方式
实施例1、注塑级产品
将稻草秸秆进行破碎,成为长度为1.5~2.0 mm的碎屑,选用硅烷偶联剂、乙撑双硬脂酸酰胺作为塑料添加剂,与注塑级聚乳酸混合后经双螺杆挤出机挤出造粒。投料时,稻草秸秆、硅烷偶联剂、乙撑双硬脂酸酰胺、注塑级聚乳酸分别占原料总质量的23~33%,1~1.5%,3~4.5%,63~73%。由此方法生产的塑料粒子可通过注塑成型,生产制造相应的注塑件。
可以通过添加聚丁二酸丁二醇酯对产品的力学性能进行调整,添加量为原料总质量的10%~75%。添加更多的聚丁二酸丁二醇酯将会使产品更加柔软。而具体的添加量需要根据不同的产品要求而确定。
由上述塑料粒子生产的制品在堆肥条件下180天,降解率达到95%以上。
实施例2、吹膜级产品
将麦草秸秆、玉米秆进行粉碎,成为1000~1200目的粉末,选用铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺、钛白粉作为塑料添加剂,与吹膜级聚丁二酸丁二醇酯混合后经双螺杆挤出机挤出造粒。投料时,麦草秸秆、玉米秆、铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺、钛白粉、吹膜级聚丁二酸丁二醇酯分别占原料重质量的10~13%,13~20%,1~2%,1.5~2%,1.5~2%,63~73%。由此方法生产的塑料粒子可通过吹膜成型,生产制造相应的膜类制品。
可以通过添加聚羟基脂肪酸酯(PHA)和聚乳酸对产品的力学性能进行调整,添加量为5~25%。添加更多的聚羟基脂肪酸酯和聚乳酸可以使产品柔软度下降。具体的添加量需要根据不同的产品需求而确定。
由上述塑料粒子制成的膜制品除了具备普通塑料薄膜的性质外,还具有良好的透气性,特别适用于透气不透水的场合,例如保鲜膜、纸尿裤内膜等。
由上述塑料粒子生产的制品在堆肥条件下180天,降解率达到95%以上。
实施例3、拉片级产品
将稻草秸秆、麦草秸秆、玉米芯、麸皮进行粉碎,成为1000~1200目的粉末,选用乙撑双硬脂酸酰胺、钛白粉作为塑料添加剂,与拉片级聚乳酸混合后经双螺杆挤出机挤出造粒。
投料时,稻草秸秆、麦草秸秆、玉米芯、麸皮、乙撑双硬脂酸酰胺、钛白粉、拉片级聚乳酸分别占原材料总质量的5~8%,5~8%,5~7%,8~10%,1.5~2%,2~4%,63~73%。
由此方法生产的塑料粒子可通过拉片成型,生产制造相应的片材制品。
可以通过添加聚己内酯(PCL)对产品的力学性能进行调整,添加量为5~15%。添加更多的聚己内酯可以使产品更加柔软。具体的添加量需要根据不同的产品需求而确定。
由上述塑料粒子生产的制品在堆肥条件下180天,降解率达到95%以上。
工业实用性
本发明一种可降解塑料及其生产方法,可形成的粒料颗粒均匀,状态稳定的可降解塑料,可代替聚丙烯等常规塑料制作日常用品、餐具、容器、文具、塑料袋等,具有良好的表面光洁度,强度高、韧性好、手感舒适。

Claims (9)

  1. 一种可降解塑料,其特征在于,由可降解塑料、农作物秸秆和塑料助剂组成,所述可降解塑料、农作物秸秆、塑料助剂分别占原料总质量的63~73%、23~33%和4~6%。
  2. 根据权利要求1所述可降解塑料,其特征在于,所述可降解塑料为聚乳酸、聚丁二酸丁二醇酯中的任意一种。
  3. 根据权利要求2所述可降解塑料,其特征在于,所述可降解塑料还包括聚羟基脂肪酸酯或聚己内酯。
  4. 根据权利要求1所述可降解塑料,其特征在于,所述农作物秸秆为稻草秸秆、麦草秸秆、麸皮、玉米芯或玉米秆中的至少任意一种。
  5. 根据权利要求1所述可降解塑料,其特征在于,所述塑料助剂为硅烷偶联剂、铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺或钛白粉中的至少任意一种。
  6. 一种如权利要求1所述的农作物塑料的生产方法,其特征在于,将长度为1.5~2.0 mm的农作物秸秆碎屑经干燥后与塑料、塑料助剂混合,经双螺杆挤出机挤出造粒;投料时,塑料、农作物秸秆、塑料助剂分别占原料总质量的63~73%、23~33%和4~6%。
  7. 根据权利要求1所述可降解塑料,其特征在于,所述农作物秸秆选用稻草秸秆,将稻草秸秆进行破碎,成为长度为1.5~2.0 mm的碎屑,选用硅烷偶联剂、乙撑双硬脂酸酰胺作为塑料添加剂,与注塑级聚乳酸混合后经双螺杆挤出机挤出造粒;投料时,稻草秸秆、硅烷偶联剂、乙撑双硬脂酸酰胺、注塑级聚乳酸分别占原料总质量的23~33%,1~1.5%,3~4.5%,63~73%。
  8. 根据权利要求1所述可降解塑料,其特征在于,所述农作物秸秆选用麦草秸秆、玉米秆,将麦草秸秆、玉米秆进行粉碎,成为1000~1200目的粉末,选用铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺、钛白粉作为塑料添加剂,与吹膜级聚丁二酸丁二醇酯混合后经双螺杆挤出机挤出造粒;投料时,麦草秸秆、玉米秆、铝酸酯/钛酸酯复合偶联剂、乙撑双硬脂酸酰胺、钛白粉、吹膜级聚丁二酸丁二醇酯分别占原料重质量的10~13%,13~20%,1~2%,1.5~2%,1.5~2%,63~73%。
  9. 根据权利要求1所述可降解塑料,其特征在于,所述农作物秸秆选用将稻草秸秆、麦草秸秆、玉米芯、麸皮进行粉碎,成为1000~1200目的粉末,选用乙撑双硬脂酸酰胺、钛白粉作为塑料添加剂,与拉片级聚乳酸混合后经双螺杆挤出机挤出造粒;投料时,稻草秸秆、麦草秸秆、玉米芯、麸皮、乙撑双硬脂酸酰胺、钛白粉、拉片级聚乳酸分别占原材料总质量的5~8%,5~8%,5~7%,8~10%,1.5~2%,2~4%,63~73%。
PCT/CN2011/073174 2011-02-28 2011-04-22 一种可降解塑料及其生产方法 WO2012116515A1 (zh)

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